Lithium battery electrodes

ABSTRACT

Electrode materials for electrochemical cells and batteries and methods of producing such materials are disclosed herein. The electrode materials comprise an active lithium metal oxide material prepared by: (a) contacting the lithium metal oxide material with an aqueous acidic solution containing one or more metal cations; and (b) heating the so-contacted lithium metal oxide from step (a) to dryness at a temperature below 200° C. The metal cations in the aqueous acidic solution comprise one or more metal cations selected from the group consisting of an alkaline earth metal ion, a transition metal ion, and a main group metal ion.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.15/909,691, filed on Mar. 1, 2018, which claims priority benefit of U.S.Provisional Application Ser. No. 62/466,070, filed on Mar. 2, 2017, eachof which is incorporated herein by reference in its entirety.

STATEMENT OF GOVERNMENT INTEREST

The United States Government has rights in this invention pursuant toContract No. DE-AC02-06CH11357 between the United States Government andUChicago Argonne, LLC representing Argonne National Laboratory.

FIELD OF THE INVENTION

This invention relates to electrode materials for electrochemical cellsand batteries. Such cells and batteries are used widely to powernumerous devices, for example, portable electronic appliances andmedical, transportation, aerospace, and defense systems.

SUMMARY OF THE INVENTION

Electrode materials (anodes and cathodes) for electrochemical cells andbatteries are described herein. In particular, metal oxide electrodematerials for lithium cells and batteries, preferablylithium-metal-oxide electrode materials, are described, whichpredominantly have layered-type structures, rock salt-type structures,or spinel-type structures, or combinations or modifications thereof.More specifically, an effective method to protect and/or enhance thesurface of the metal oxide or lithium metal oxide electrode materials isdescribed. For example, a solution of a strong acid such as nitric acid,containing at least one stabilizing metal cation, such as aluminum,zirconium, magnesium, cobalt or nickel, is applied to the surface of themetal oxide or lithium metal oxide, thereby protecting the surface ofthe electrode materials from undesirable effects in electrochemicalcells, such as electrolyte oxidation, oxygen loss, and/or dissolution.Such surface protection/coating significantly enhances the surfacestability, rate capability and cycling stability of the electrodes,which leads to increased electrode capacity and energy of the cells.Surface protected electrode materials made by the method, preferably forlithium- or lithium-ion cells and batteries, also are described. Theelectrodes and electrode materials described herein can be used eitherin primary or rechargeable cells and batteries.

In one aspect, the electrode materials comprise a layered-typestructure, a spinel-type structure, a rock salt-type structure, or acombination of these structure types, for example, anintegrated/composite structure comprising one or more of these structuretypes. As used herein, layered compounds and structures refer broadly tolithium metal oxides of formula Li_(z)MO_((z+1)) (z=1 or 2) orsubstituted derivatives thereof, in which M is one or more metal ions(e.g., transition metals), the structures of which comprise alternatinglayers of lithium ions interspersed with layers containing other metalions, M. The layers containing the M metal ions preferably containlithium ions such that the Li:M ratio is >1 (e.g., 1.001 to 2), in whichcase the electrode is considered to be lithium rich. In an additionalpreferred embodiment, the M cations comprise manganese, nickel and/orcobalt ions such that the Mn content is greater than, or equal to, theNi content or greater than the nickel plus cobalt content, in whichcases, the electrode is considered to be manganese rich. In yet anotherpreferred embodiment, the electrode is both lithium and manganese rich.

Typical non-limiting examples of layered cathode materials in theirpristine, untreated state include, for example, by layeredLi_(z)MO_((z+1)), where z=1 or 2, and M is, e.g., Mn, Ni and Co, such asLiCoO₂ in which layers of lithium ions alternate with layers of cobaltions in a close-packed oxygen array; and Li₂MnO₃ in which layers oflithium alternate with layers of manganese and lithium ions in aclose-packed oxygen array. Rock salt compounds and structures orcomponents of structures, include, e.g., M′O, in which the M′ to O ratiois ideally 1:1, and in which M′ is one or more metal ions (includinglithium) that have close-packed structures. Additionally, M′O componentswithin layered or spinel structures, e.g., NiO, also are included withinthe present methods and materials. Spinel compounds and structures referbroadly to the family of close-packed lithium metal oxides, Li[M″₂]O₄,in which the metal:oxygen (Li+M″):O ratio ideally is 3:4 (i.e., 0.75:1),or cation or anion substituted derivatives thereof, in which M″ is oneor more metal ions, as exemplified by the spinel cathode systemLi_(1+n)Mn_(2−n)O₄(0≤n≤0.33) and the lithium titanate anode systemLi₄Ti₅O₁₂ (Li[Li_(1/3)Ti_(5/3)]O₄ and substituted derivatives thereof.Lithiated spinel compounds refer to Li₂[M″₂]O₄, e.g., where M″=Mn, Co,Ti and the like, and substituted derivatives thereof.

It is to be understood that, in practice, deviations from idealcrystallographic behavior of these structure types are commonplace, suchas variations in composition, in atomic positions and coordination siteswithin crystal structures, as well as in the site occupancy of atoms andin the structural disorder of atoms on different sites. Suchcrystallographic deviations and imperfections that can give rise tonon-ideal cation arrangements in stoichiometric and/or defect layered,spinel and rock salt components of the electrode structures,particularly at grain or particle boundaries, within or at the surfaceof individual component structures, are therefore necessarily includedwithin the definitions provided above and within the spirit and scope ofthis invention. Generally speaking, the compositional and structuralspace of the electrodes of this invention can be defined and representedby phase diagrams of layered, spinel and rock salt structures, allowingfor crystallographic imperfections such as cation disorder, stackingfaults, and structural defects and vacancies, for example, localizednon-stoichiometry, as described above.

A unique aspect of the surface treatment method described herein is thatthe method has been discovered to work remarkably effectively at lowheating and drying temperatures, e.g., approximately 100° C. or slightlyhigher (e.g., about 110° C.), for selected compositions and structures,and particularly for lithium- and manganese-rich lithium metal oxideelectrode compositions and structures that are comprised of lithium,manganese and nickel ions in which the manganese content is higher than,or equal to, the nickel content.

Non-limiting examples of certain embodiments of the methods andmaterials described herein include:

Embodiment 1, which is a method of preparing an active lithium metaloxide material suitable for use in an electrode for a lithiumelectrochemical cell, the method comprising the steps of: contacting thelithium metal oxide material with an aqueous acidic solution containingone or more metal cations; and heating the so-contacted lithium metaloxide from step (a) to dryness at a temperature below 200° C.; andwherein the metal cations in the aqueous acidic solution comprise one ormore metal cations selected from the group consisting of an alkalineearth metal ion, a transition metal ion, and a main group metal ion.

Embodiment 2, which is the method of embodiment 1, wherein thetemperature in step (b) is less than 150° C.

Embodiment 3, which is the method of embodiment 1, wherein thetemperature in step (b) is less than 120° C.

Embodiment 4, which is the method of embodiment 1, wherein thetemperature in step (b) is 100° C. or less.

Embodiment 5, which is the method of embodiment 1, wherein the aqueousacidic solution has a pH in the range of about 4 to about 7.

Embodiment 6, which is the method of embodiment 1, wherein the lithiummetal oxide material in step (a) is a compound with a layered structure,a spinel structure, a rock salt structure, a blend of two or more of theforegoing structures, or a structurally-integrated composite of two ormore of the foregoing structures.

Embodiment 7, which is the method of embodiment 6, wherein the lithiummetal oxide material comprises a compound with a structurally-integrated‘layered-layered’ structure comprising xLi₂MnO₃.(1−x)LiMO₂ or a‘layered-layered-spinel’ structure comprisingy[xLi₂MnO₃.(1−x)LiMO₂].(1−y)LiM″₂O₄, in which M and M″ comprise one ormore metal ions for 0<x<1 and 0<y<1.

Embodiment 8, which is the method of embodiment 7, wherein one or moreof the structures of the lithium metal oxide electrode are imperfect andcharacterized by one or more imperfections including cation disorder,stacking faults, dislocations, structural defects and vacancies, andlocalized non-stoichiometry.

Embodiment 9, which is the method of embodiment 7, wherein the Li, Mn,M, and M″ cations are partially disordered over octahedral andtetrahedral sites of the layered and spinel components of the lithiummetal oxide structure.

Embodiment 10, which is the method of embodiment 7, wherein M and M″comprise one or more metals selected from of Mn, Ni, and Co, andoptionally, one or more other metals selected from Al, Mg and Li.

Embodiment 11, which is the method of embodiment 7, wherein the lithiummetal oxide material comprises Mn and Ni in an atomic ratio of Mn:Nigreater than or equal to 1.

Embodiment 12, which is the method of embodiment 7, wherein the lithiummetal oxide material comprises Mn, Ni and Co in an atomic ratio ofMn:(Ni+Co) greater than or equal to 1.

Embodiment 13, which is the method of embodiment 1, wherein the metalcations in the aqueous acidic solution comprise one or more metalcations selected from the group consisting of aluminum ion, magnesiumion, cobalt ion, and nickel ion.

Embodiment 14, which is the method of embodiment 1, wherein the metalcations in the aqueous acidic solution comprise one or more metalcations selected from the group consisting of zirconium and aluminumions.

Embodiment 15, which is the method of embodiment 1, wherein the aqueousacidic solution is a metal nitrate solution.

Embodiment 16, which is the method of embodiment 15, wherein the metalnitrate comprises aluminum nitrate, zirconium nitrate or a combinationthereof.

Embodiment 17, which is an electrode for a non-aqueous electrochemicalcell comprising an active lithium metal oxide material prepared by themethod of embodiment 1.

Embodiment 18, which is the electrode of embodiment 17, in which theactive lithium metal oxide material exhibits a peak of about 531.5 eVadjacent a peak at about 529.5 eV in an X-ray photoelectron spectroscopy(XPS) spectrum of the material.

Embodiment 19, which is an electrochemical cell comprising a cathode, ananode, a separator membrane between the cathode and the anode, and alithium-containing electrolyte contacting the anode, the cathode, andthe membrane, wherein either the anode or the cathode is the electrodeof embodiment 17.

Embodiment 20, which is the electrochemical cell of embodiment 19,wherein the electrolyte comprises up to about 1 percent by weight (e.g.,about 0.01 to about 1 wt %; or 0.05 to about 0.75 wt %; or about 0.1 toabout 0.5 wt %) of lithium difluoro(oxalate)borate (LiDFOB).

Embodiment 21, which is a battery containing more than oneelectrochemical cell of embodiment 19, connected in series, in parallel,or in both series and parallel.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention consists of certain novel features and a combination ofparts hereinafter fully described, illustrated in the accompanyingdrawings, it being understood that various changes in the details may bemade without departing from the spirit, or sacrificing any of theadvantages of the present invention.

FIG. 1 depicts capacity versus cycle number plots for untreated (opensymbols) and Al-treated (closed symbols) ‘layered-layered-spinel’ (LLS)electrodes in Li half-cells when cycled between 4.5 V and 2.5 V after afirst-cycle activation between 4.6 and 2.0 V (15 mA/g, 30° C.).

FIG. 2 depicts capacity versus cycle number plots for Al-treated, LLSelectrodes in Li half-cells cycled between 4.5 and 2.5 V after afirst-cycle activation between 4.6 and 2.0 V (15 mA/g, 30° C.); sampleswere treated at 110° C. (closed circles, this invention), 400° C. (opencircles), or 550° C. (diamonds).

FIG. 3 depicts capacity versus cycle number plots for Al-treatedelectrodes, (a) NMC-532, (b) NMC-442, and (c) baseline LLS(Mn:Ni:Co=0.47:0.25:0.17) in Li half-cells cycled between 4.5 and 2.5 Vafter a first-cycle activation between 4.6 and 2.0 V (15 mA/g, 30° C.);all Al-treatments were performed (dried) at 110° C.

FIG. 4 depicts electrochemical profiles of lithium half cells containingan untreated ‘layered-layered’ (LL)0.25Li₂MnO₃.0.75LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂ electrode (left), anuntreated, underlithiated LLS derivative of LL0.25Li₂MnO₃.0.75LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂ (middle), and anAl-surface treated LLS derivative of LL0.25Li₂MnO₃.0.75LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂ (right).

FIG. 5 depicts corresponding dQ/dV plots of the electrochemical profilesin FIG. 4.

FIG. 6 depicts capacity versus cycle number plots for lithium half cellswith a parent LL (untreated) electrode (bottom), an underlithiated,untreated LLS electrode (2^(nd) from bottom), an underlithiated,Al-surface-treated LLS electrode (2^(nd) from top) when cycled between4.5 and 2.5 V after a first-cycle activation between 4.6 and 2.0 V (15mA/g, 30° C.); and an underlithiated, Al-surface-treated LLS electrodewhen cycled continuously between 4.6 and 2.5 V after a first-cycleactivation between 4.6 and 2.0 V (15 mA/g, 30° C.) (top).

FIG. 7 depicts the XPS data of LLS electrodes after Al-treatment anddrying/annealing at various temperatures.

FIG. 8 shows (a) a plot of discharge capacity versus cycle number forLLS//Gr cells cycled with LiDFOB as an additive from 0-3% (wt.); and (b)coulombic efficiencies for the cells shown in (a); at 4.4-2.5V vs.graphite, C/2 ageing cycles, 3-hour holds at the top of each charge;breaks in the cycling data represent diagnostic cycles for collectingimpedance data

FIG. 9 depicts area specific impedance (ASI, Ω·cm²) for LiDFOBcontaining cells: (a) 0% LiDFOB; (b) 1 wt % LiDFOB; and (c) 3 wt %LiDFOB.

FIG. 10 depicts (a) capacity versus cycling data for un-treated LLScompared with Al-treated LLS with and without 0.5% (wt.) LiDFOB as anadditive against graphite anodes; and (b) coulombic efficiencies for thecells shown in (a); at 4.4-2.5V vs. graphite, C/2 ageing cycles, 3-hourholds at the top of each charge; breaks in the cycling data representdiagnostic cycles for collecting impedance data.

FIG. 11 shows area specific impedance (ASI, Ω·cm²) for (a) untreatedLLS//Gr cells; (b) Al treated LLS//Gr cells; and (c) Al treated LLS//Grcells containing 0.5 wt % LiDFOB.

FIG. 12 provides dQ/dV plots of the first cycle charge of LLS//Gr cellscontaining Al-treated LLS with and without LiDFOB additive as marked inthe legend.

FIG. 13 illustrates (a) capacity versus cycle number for LLS//Li cellswhere the LLS powders have been treated with stoichiometric amounts ofAl_(1.85)Mg_(0.15)O_(x), Al_(1.85)Ni_(0.15)O_(x), andAl_(1.85)Co_(0.15)O_(x) using nitrate precursors in aqueous solution,followed by annealing at about 110° C.; and (b) capacity normalized tothe 5th cycle.

FIG. 14 depicts a schematic representation of an electrochemical cell.

FIG. 15 depicts a schematic representation of a battery consisting of aplurality of cells connected electrically in series and in parallel.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

State-of-the-art lithium-ion battery electrode materials do not meetnext-generation targets for transportation applications. The highlycorrelated parameters of energy and lifetime are of particularsignificance and still need to be greatly improved. Several strategiesto improve energy densities have been pursued including theincorporation of “excess” capacity, relative to typical layeredLi_(z)MO_((z+1)) (z=1 or 2, M=Mn, Ni, Co), spinel LiMn₂O₄, and olivineLiFePO₄ cathode materials. Specifically, the integration of layeredLi₂MnO₃ to create structurally-integrated composite ‘layered-layered’electrode structures (e.g., xLi₂MnO₃.(1−x)LiMO₂, where 0<x<1 and 0<y<1)has shown particular promise for enhancing the energy content of lithiumcells. However, ‘layered-layered’ electrodes undergo structuraltransformations with cycling leading to a large irreversible first-cyclecapacity, surface damage, and modification of the discharge and chargevoltage profile with cycling, commonly referred to as voltage fade.Voltage fade causes a cycle-to-cycle decrease in the average energyoutput of cells and is a challenge yet to be overcome. The incorporationof local spinel, or spinel-like, configurations to form multi-component,structurally-integrated ‘layered-layered-spinel’ electrode materialssuch as y[xLi₂MnO₃.(1−x)LiMO₂].(1−y)LiM″₂O₄ (where 0<x<1, 0<y<1, and Mand M″ are predominately transition metals) has shown promise inaddressing some of these limitations and to access higher capacities athigh charging potentials (>4.4 V vs. Li⁰), which is above the typicalupper charging limit of commercial lithium-ion cells. Specifically, thefirst-cycle efficiency can be increased, the rate capability improved,and the voltage fade mitigated, at least to some extent. Despite theseimprovements, a major challenge that remains is to stabilize thesurfaces of these cathode materials at high potentials during charge atwhich electrode/electrolyte reactions can lead to impedance rise, lossof electrochemically active lithium, and shortened cell lifetimes.

Note that the rock salt compounds and structures, or components ofstructures, referred to in this specification relate broadly to metaloxides, M′O, in which the M′ to O ratio ideally is 1:1 and in which M′is one or more metal ions (including, e.g., transition metals andlithium) that have close-packed structures typified, for example, bylayered Li_(z)MO_((z+1)) compounds (z=1 or 2, M=Mn, Ni, Co, etc.),lithiated spinel compounds (e.g., Li₂[M″₂]O₄, where M″=Co, Ti) andsubstituted derivatives thereof, and by M′O components within layeredand lithiated spinel structures, e.g., NiO. Spinel compounds andstructures refer broadly to the family of close-packed lithium metaloxides, e.g., Li[M″₂]O₄, or cation or anion substituted derivativesthereof, in which the (Li+M″):O ratio is ideally 3:4 (i.e., 0.75:1).Examples of Li[M″₂]O₄ spinel anode and cathode electrode structures, inwhich M″ is one or more metal ions (e.g., Mn, Ti and the like), are thespinel cathode system Li_(1+n)Mn_(2−n)O₄ (0≤n≤0.33) and the lithiumtitanate anode system Li₄Ti₅O₁₂ (Li[Li_(1/3)Ti_(5/3)]O₄, and substitutedderivatives thereof. It therefore stands to reason thatstructurally-integrated electrode structures such asxLiMO₂.(1−x)Li[M″₂]O₄ (where 0<x<1) will ideally have a total(Li+M+M″):O ratio between 1:1 and 0.75:1. In practice, however, thevariations in the oxygen content may be accommodated by changes in theoxidation state of the M cations, thereby making a precise determinationof the total metal to O ratio in the electrodes of this inventiondifficult.

In a further embodiment, the lithium metal oxide electrode structuresproduced by the methods described herein can be imperfect andcharacterized by one or more imperfections, for example, cationdisorder, stacking faults, dislocations, structural defects andvacancies, and localized non-stoichiometry.

One preferred embodiment is a processing method to modify the surfaceand enhance the surface stability of lithium metal oxide cathodematerials with layered, spinel or multi-component combinations thereofas described above, for primary or secondary lithium cells andbatteries, or lithium-ion cells and batteries. Important features ofthis processing method, relative to typical strategies, are: (1) thecompositional-dependence for which surface modifications proveeffective; (2) treatment of layered, ‘layered-layered’, and‘layered-layered-spinel’ cathodes under acidic conditions to improve,symbiotically, surface stability and first-cycle efficiency; and (3) theuse of low temperature heating/drying step, at or below 200° C.,preferably below approximately 150° C., more preferably belowapproximately 120° C., and most preferably at approximately 100° C. orbelow, optionally under vacuum, that lead to novel and effective surfacestructures. The duration of the heating step should be as short aspossible, preferably less than approximately 24 hours, more preferablyless than approximately 12 hours, and most preferably less thanapproximately 8 hours or shorter. The surface treatment of theelectrodes under acidic conditions preferably takes place in thepresence of nitrate ions and one or more soluble, surface stabilizingmetal cations, for example, aluminum and/or zirconium ions.

A unique aspect of the method described herein is that the surfacetreatment method has been discovered to work effectively for selectedcompositions and structures, and particularly for lithium andmanganese-rich lithium metal oxide electrode compositions and structuresthat are comprised of lithium, manganese and nickel ions in which themanganese content is higher than, or equal to, the nickel content.Likewise, in another embodiment, lithium and manganese-rich lithiummetal oxide electrode compositions and structures comprised of lithium,manganese, nickel and cobalt ions are preferred when the manganesecontent is higher than, or equal to, the combined nickel and cobaltcontent (based on atomic ratios of the metals).

Another embodiment of the present method is to modify the surface andenhance the surface stability of lithium metal oxide anode materialswith layered and spinel structures, as described above, for example, alithium titanate spinel, Li₄Ti₅O₁₂, or substituted variations thereof,that are known to undergo gassing at the surface during electrochemicalreactions.

In another aspect, electrochemical cells comprising the treated cathodematerials are enhanced by addition of small amounts (e.g., about 0.01 toabout 0.5 wt %) of additives such as LiDFOB to the electrolyte. TheLiDFOB has a surprising synergistic effect with the low temperaturemetal surface treatments described herein to markedly improve theperformance of the Al-treated cells. For example, capacity retention andcoulombic efficiencies are improved over the baseline and Al-treatedcells without LiDFOB, and impedance rise is curtailed with the LiDFOBadded to the electrolyte in combination with the surface treatment ofthe cathode material, especially with structurally-integrated compositemetal oxides such as ‘layered-layered’ (LL), ‘layered-spinel’ (LS) and‘layered-layered-spinel’ lithium metal oxide materials, which are wellknown in the art; e.g., an LLS such as0.25Li₂MnO₃.(1−x)LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂, with a targeted 15%spinel content.

As used herein, a structurally-integrated composite metal oxide is amaterial that includes domains (e.g., locally ordered, nano-sized ormicro-sized domains) indicative of different metal oxide compositionshaving different crystalline forms (e.g., layered or spinel forms)within a single particle of the composite metal oxide, in which thedomains share substantially the same oxygen lattice and differ from eachother by the elemental and spatial distribution of metal ions in theoverall metal oxide structure. Structurally-integrated composite metaloxides are different from and generally have different properties thanmere mixtures of two or more metal oxide components (for example, meremixtures do not share a common oxygen lattice).

The lithium metal oxide materials can be incorporated in a lithium ionelectrochemical cell in a positive electrode (cathode) or a negativeelectrode (anode). Such cells also typically include a separator betweenthe cathode and anode, with an electrolyte in contact with both theanode and cathode, as is well known in the battery art. A battery can beformed by electrically connecting two or more such electrochemical cellsin series, parallel, or a combination of series and parallel.Electrochemical cell and battery designs and configurations, anode andcathode materials, as well as electrolyte salts, solvents and otherbattery or electrode components (e.g., separator membranes, currentcollectors), which can be used in the electrolytes, cells and batteriesdescribed herein, are well known in the lithium battery art, e.g., asdescribed in “Lithium Batteries Science and Technology” Gholam-AbbasNazri and Gianfranco Pistoia, Eds., Springer Science+Business Media,LLC; New York, N.Y. (2009), which is incorporated herein by reference inits entirety.

Example 1

A ‘layered-layered-spinel’ electrode, was synthesized as described byLong et al. in the Journal of the Electrochemical Society, Volume 161,pages A2160-A2167 (2014) by underlithiating a composition of a nominal‘layered-layered’ Li_(1.11)Mn_(0.47)Ni_(0.25)Co_(0.17)O₂ material(alternatively, in composite notation,0.25Li₂MnO₃.0.75LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂ or normalizednotation, Li_(1.25)Mn_(0.53)Ni_(0.28)Co_(0.19)O_(2.25) to produce a‘layered-layered-spinel’ composition with a targeted 15% spinel contentwith respect to a ‘layered-layered-spinel’ compositional phase diagramin which the Mn:Ni:Co ratio was 0.47:0.25:0.17 and in which the Li tototal M (Mn+Ni+Co) ratio was >1. The ‘layered-layered-spinel’ materialwas subsequently treated in an acidic aluminum nitrate solution followedby drying the product in air at approximately 110° C. for approximately12 hours without a higher temperature annealing step, in accordance withthe principles of this invention. FIG. 1 shows capacity vs. cycle numberplots for the untreated (open symbols) and Al-treated (closed symbols),‘layered-layered-spinel’ electrode materials in Li half-cells betweenabout 4.5 and about 2.5 V after a first-cycle activation between about4.6 and about 2.0 V (15 mA/g, 30° C.).

The electrode material dried at 110° C. shows a significant increase incapacity as well as a superior capacity retention over more than 40cycles relative to the untreated, baseline ‘layered-layered’ electrodematerial. In addition, the incorporation of a spinel component in‘layered-layered’ electrodes significantly increases the first-cycleefficiency to about 92%, relative to the lower first-cycle efficiency ofabout 78% for a parent ‘layered-layered’ electrode with nominalcomposition Li_(1.25)Mn_(0.53)Ni_(0.28)Co_(0.19)O₂ (alternatively, in‘layered-layered’ composite notation,0.25Li₂MnO₃.0.75LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂), as disclosed by Longet al. in the Journal of the Electrochemical Society publication,referenced above. As shown FIG. 1, the acidic Al-treatment of theelectrode, further increases the first-cycle efficiency to about 94%, onpar or better than state-of-the-art, layeredlithium-nickel-manganese-cobalt-oxide (NMC) electrodes. The improvedefficiency may be attributed to (1) better surface protection due tomitigated electrolyte interactions and/or (2) an unexpected symbioticprocess of the acidic solution in leaching small amounts of Li and/oroxygen from the electrode surface. The leaching action described inpoint (2) above mimics the first-cycle electrochemical activationprocess well-known for Li- and Mn-rich materials in ‘layered-layered’xLi₂MnO₃. (1−x)LiMO₂ (M=Ni, Mn and/or Co) systems. However, incombination with a ‘layered-layered-spinel’ electrode, the acid leaching(chemical activation) process helps to balance the inherent first-cyclelithium losses (due to activation of the Li-rich component, e.g., lossof Li₂O) and the amount of “extra” capacity that can be taken up ondischarge by vacant lithium sites inherent to the integrated spinel orspinel-like component.

Example 2

A unique, unexpected aspect of the method described herein is thecombination of using (1) an aluminum nitrate solution to treat thesurface of the lithium-metal-oxide electrode particles, (2) a relativelylow drying temperature of approximately 110° C., and (3) a specificallydefined lithium-metal-oxide electrode composition, which is lithium-richand manganese-rich relative to the nickel (or nickel and cobalt)content, that significantly enhances the electrochemical properties ofthe electrode materials described and defined herein. For example, FIG.2 shows capacity vs. cycle no. plots of the ‘layered-layered-spinel’baseline electrode used for this investigation (FIG. 1), in which (a)the Mn:Ni:Co ratio is 0.47:0.25:0.17 and (b) the Li to total M ratiois >1 after treatment with an aluminum nitrate solution, followed bypost-treatment annealing in air at 400° C. and 550° C., i.e., attemperatures typically used in the art to produce Al-protected surfacelayers relative to the capacity vs. cycle no. plot of the same electrodewhen heated only to 110° C. in accordance with the principles of thisinvention. FIG. 2 clearly demonstrates that annealing the electrodes at400 and 500° C. adversely affects the performance of the lithium cellsin terms of a degradation of capacity (energy) generation and cyclingstability, whereas the electrodes dried at about 110° C., providesignificantly enhanced capacity as well as superior cycling stability.

Example 3

FIG. 3 shows how changing the composition, particularly the Li:M(M=Mn+Ni+Co) and Mn:Ni ratios in standard NMC electrode materials suchas LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂ (NMC-‘532’, FIG. 3, Panel (a) andLiNi_(0.4)Mn_(0.4)Co_(0.2)O₂ (NMC-‘442’, FIG. 3, Panel (b)) and howlow-temperature (110° C.) Al-treatment impacts their electrochemicalproperties relative to ‘layered-layered-spinel’ electrodes of thisinvention, such as the lithium- and manganese-rich electrode,Li_(1.1−y)Mn_(0.47)Ni_(0.25)Co_(0.17)O_(y) (FIG. 3, Panel (c)).

FIG. 3 clearly demonstrates that for the nickel-rich electrodes in whichthe Ni:Mn ratio is 5:3 and 1:1 (FIG. 3, Panels (a) and (b)),respectively, the Al-treatment is not as effective as it is for thelithium- and manganese-rich electrode in FIG. 3, Panel (c), the latterelectrode providing a significantly higher rechargeable electrodecapacity (about 210-215 mAh/g) than the nickel-rich electrodes (about195 mAh/g) when cycled in Li half-cells cycled between 4.5 and 2.5 Vafter a first-cycle activation between 4.6 and 2.0 V (15 mA/g, 30° C.).Of particular note is that layered NMC-based materials, including LiCoO₂and LiMn_(0.5)Ni_(0.5)O₂ also require surface protection in order tomitigate chemical and electrochemical interactions at theelectrode/electrolyte interface. Furthermore, NMC electrodes aregenerally known to cycle well in Li half-cells, as shown by theperformance of cells with untreated electrodes in FIG. 3, Panels (a) and(b). In particular, FIG. 3, Panel (b) indicates that Al-treatment ofLiNi_(0.4)Mn_(0.4)Co_(0.2)O₂ (Ni:Mn=1:1) at 110° C. does not limit therechargeable capacities as it does in LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂(Ni:Mn=1.67) in FIG. 3, Panel (a), and therefore can be a viable optionfor treating electrode materials with a high Mn content relative to Ni,and layered LiCo_(1−x)Ni_(x)O₂ materials with a Co:Ni greater than 1:1(i.e., 0≤x<0.5), including LiCoO₂. FIG. 3, Panel (c) clearlydemonstrates that the lithium- and manganese-rich‘layered-layered-spinel’ electrode composition with a Mn:Ni ratio ofapproximately 2:1 benefits from the low-temperature, acidic Al-treatmentin accordance with the methods described herein.

Example 4

The electrochemical profiles of lithium half cells containing a parent‘layered-layered’ electrode of nominal composition0.25Li₂MnO₃0.75LiMn_(0.375)Ni_(0.37)Co_(0.375)O₂ (alternatively, innormalized notation, Li_(1.11)Mn_(0.47)Ni_(0.25)Co_(0.17)O₂) andunderlithiated ‘layered-layered-spinel’ derivatives containing atargeted 15% spinel content, one of which was subjected to Al-surfacetreatment in an acidic aluminum nitrate solution followed by drying inair at about 110° C., are shown in FIG. 4. Li half-cells were cycledbetween 4.5 and 2.5 V after a first-cycle activation between 4.6 and 2.0V (15 mA/g, 30° C.). In FIG. 4, electrochemical profiles of lithium halfcells containing an untreated ‘layered-layered’ electrode material(0.25Li₂MnO₃.0.75LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂ (left)), anuntreated, underlithiated ‘layered-layered-spinel’ derivative(‘layered-layered’ 0.25Li₂MnO₃.0.75LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂(middle)), and an Al-surface treated ‘layered-layered-spinel derivative(‘layered-layered’ 0.25Li₂MnO₃.0.75LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂(right)). Corresponding dQ/dV plots of the electrochemical profiles areprovided in FIG. 5.

The electrochemical data in FIG. 4 and FIG. 5 clearly demonstrate theimprovement in electrochemical capacity that can be gained by creating a‘layered-layered-spinel’ electrode by underlithiating a parent‘layered-layered’ electrode composition, as already disclosed by Long etal. However, the additional capacity that can be gained by surfacetreatment of the ‘layered-layered-spinel’ electrode as taught herein toyield a capacity close to 220 mAh/g, is remarkable because it opens thedoor for further exploitation and improvement. Indeed, widening theoperating voltage window to allow continuous cycling of the lithium halfcell between 4.6-2.5 V, after a first-cycle activation between 4.6 and2.0 V (15 mA/g, 30° C.), increases the delivered capacity to almost 230mAh/g, as shown in the capacity vs. cycle number plots in FIG. 6 for thefirst 14 cycles: capacity vs. cycle number plots for lithium half cellswith a parent ‘layered-layered’ (untreated) electrode (bottom), anunderlithiated, untreated ‘layered-layered-spinel’ electrode (2nd frombottom), an underlithiated, Al-surface-treated ‘layered-layered-spinel’electrode (2nd from top) when cycled between 4.5 and 2.5 V after afirst-cycle activation between 4.6 and 2.0 V (15 mA/g, 30° C.); and anunderlithiated, Al-surface-treated ‘layered-layered-spinel’ electrodewhen cycled continuously between 4.6 and 2.5 V after a first-cycleactivation between 4.6 and 2.0V (15 mA/g, 30° C.) (top).

Example 5

Two baseline structurally-integrated ‘layered-layered-spinel’ electrodematerials (labeled: LLS_baseline_1 & LLS_baseline_2) prepared bydifferent methods were treated with the same aluminum surface treatment.After the initial aluminum treatment, the samples were heated todifferent temperatures. The samples were analyzed by X-ray photoelectronspectroscopy (XPS). FIG. 7 summarizes the O is spectra for each series.In each series, the sample treated at 100° C. exhibits a distinct peaknear 531.5 eV (near the reported value of O binding energy in Al₂O₃)when compared to samples treated at higher temperatures and with respectto the baseline.

Table 1 summarizes the surface composition (atomic %) of each sample inthe series. The analyses indicate that (1) the data obtained from thetwo samples are generally in excellent agreement with one another; (2)there is no aluminum in the baseline samples; (3) the aluminumconcentration at the surface of the treated samples decreases as theprocessing temperature is increased above approximately 100° C.; (4) themagnitude of the XPS peak at approximately 531.5 eV (adjacent to arelatively intense peak at approximately 529.5 eV) is strongest for thebest performing Al-treated electrodes that had been dried atapproximately 100° C., indicating that the XPS technique can be used asa quality control yardstick to identify optimum surface compositions andsurface-treatment temperatures for the electrode materials of thisinvention.

TABLE 1 Surface analyses of various layered-layered-spinel (LLS) samplesby XPS, with values expressed as atomic percentages (at. %). SurfaceComposition (at. %) Al Li Ni Mn Co O C Na N B.E-Al LLS_baseline_1 0.027.0 5.3 5.8 2.6 34.0 19.2 6.1 0.0 — Al_100 C._LLS_1 3.51 26.9 5.0 5.72.1 38.1 14.8 3.5 0.4 73.8 Al_400 C._LLS_1 2.58 28.9 4.9 6.1 2.2 34.713.9 6.0 0.7 73.3 Al_550 C._LLS_1 1.91 26.1 5.7 6.3 2.8 36.5 13.1 7.20.5 72.8 LLS_baseline_2 0.0 23.4 5.4 6.6 2.8 36.6 19.7 5.6 0.0 — Al_100C._LLS_2 3.0 25.1 5.2 5.5 2.1 39.5 16.2 3.1 0.5 73.8 Al_550 C._LLS_2 1.724.0 5.4 5.9 2.4 37.0 18.3 5.3 0.0 73.0 Al_750 C._LLS_2 0.6 21.6 4.9 5.92.3 34.6 25.1 5.0 0.0 74.7

Example 6

One unique aspect of the low temperature (e.g., <200° C.) surfacetreatment described herein is that it unexpectedly displays a surprisingsynergy when used in combination with certain additives. In particular,the performance of the additive LiDFOB (lithium difluoro(oxalate)borate)is dramatically improved in combination with the low temperaturealuminum treatment. Moreover, this additive performed best incombination with the Al surface treatment when used in very lowconcentrations of just 0.5 wt %. Although LiDFOB is a previously knownadditive, reports have shown that, in combination with GEN2-typeelectrolytes (e.g., 1.2 M LiPF₆ in EC:EMC; 3:7 w/w), as much as 2%LiDFOB is needed to optimize the performance of lithium- andmanganese-rich electrodes (e.g., LL or LLS materials). See Zhue et al.,J. Electrochem. Soc., 159, A2109 (2012). Furthermore, even with theoptimized amount of LiDFOB (e.g., 2%), the impedance of such cellsreportedly still increased significantly after cycling. The same authorshave also reported that the additive LiDFOB does not significantlyimprove impedance rise and may, in some cases, negatively impact it. SeeAbraham et al., J. Power Sources, 15, 612 (2008).

FIG. 8, Panel (a), shows the cycling performance of LLS//Gr cells cycledwith LiDFOB as an additive in concentrations of 0, 0.5, 1.0, and 3.0 wt% without any surface treatment of the LLS cathode material (“baseline”LLS=0.25Li₂MnO₃.(1−x)LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂, with a targeted15% spinel content; and Gr=graphite). Clearly the addition of LiDFOBimproved the capacity performance of cells, however, as much as 3 wt %was needed for optimal performance. In addition, FIG. 8, Panel (b),shows that as the additive wt % is increased, coulombic efficienciesdecrease, indicating an increase in unwanted side reactions associatedwith additional LiDFOB.

FIG. 9, Panels (a)-(c), show discharge impedance as a function of cyclenumber for LiDFOB containing cells. It is noteworthy that increasingconcentrations of LiDFOB led to decreasing impedance rise, with the 3%LiDFOB showing the best performance, in agreement with the cycling dataof FIG. 8. However, even the optimized (3 wt %) cells showed an increaseof impedance that is nearly double the initial value. The 1 wt % LiDFOBcells showed significant impedance rise with cycling. Clearly, asreported, the LiDFOB additive alone (i.e., without the surface treatmentdescribed herein) does not eradicate impedance in these cells and largerconcentrations are needed to realize substantial improvements; however,at the cost of lower efficiencies.

FIG. 10 shows capacity vs cycling data for un-treated LLS compared withAl-treated LLS with and without 0.5% (wt.) LiDFOB as an additive againstgraphite anodes. As per the invention, the low-temperature Al treatmentalone significantly improves the cycling performance of the LLS//Grcells. Surprisingly, the addition of just 0.5 wt % LiDFOB markedlyimproves the performance of the Al-treated cells. Furthermore, thecoulombic efficiencies of FIG. 10, Panel (b), are also improved over thebaseline and Al-treated cells. Notably, the efficiencies of theAl/LiDFOB combination are the highest of all cells, including the LiDFOBonly cells. Clearly there is a unexpected synergistic relationshipbetween the low temperature Al treatment and very small amounts (e.g.,0.5 wt %) of the additive LiDFOB, where the combination improves bothcapacity retention and impedance with cycling beyond the individualtreatments. Of particular note is the impedance. As shown in FIG. 11,the impedance rise with cycling for the Al-treated samples, whileimproved over the untreated samples, displays a measurable rise underthis relatively harsh protocol (e.g., 3 hour holds at the top of eachageing cycle). However, as shown in FIG. 11, Panel (c), the combinationof the low temperature Al treatment and just 0.5 wt % LiDFOB not onlylowers the initial impedance, but also no observable rise in impedancewas evident over the approximate 100 cycles tested for impedance. Thisis clearly in contrast with the cells having no Al treatment and LiDFOBas an additive, in any wt % tested. Therefore, the improved performanceof these cells can only be attributed to the surprising synergisticinteraction of the two treatments; low temperature Al and lowconcentrations of LiDFOB.

FIG. 12 shows dQ/dV plots of the first formation cycles of LLS//Gr cellswith and without Al treatment and LiDFOB additive. The baseline,untreated (dash-dot line) shows a fairly featureless profile except forthe large, convoluted, double peak at about 3.0 V. This peak does notappear on subsequent cycles (not shown for clarity) and thus representsan irreversible reaction, likely tied to decomposition of surface phaseson the baseline electrode. Several changes were observed for the samplesthat received the low temperature Al treatment (dotted line). First, anew decomposition peak appeared at about 2.4 V and subsequently, thelarge decomposition peak at about 3.0 V was significantly suppressed.This data reiterates the ability of the low temperature Al treatment toalter the surface chemistry of the baseline LLS cathode. The addition of0.5 wt % LiDFOB to the baseline cells (solid line) resulted in a peakjust above 2.0 V. This peak was not present in the baseline and thussignals the decomposition of the additive. However, the LiDFOB did notsignificantly affect the large peak at about 3.0 V as in the case of theAl treatment. The combination of the Al treatment and 0.5 wt % LiDFOBresulted in the decomposition of the additive along with the Al-relatedprocess at about 2.4 V, which was shifted to slightly higher potential,and the suppression of the reaction that occurs at about 3.0 V.

Based on this data it is believed that the low temperature metaltreatments, along with their ability to enhance cathode surfaceproperties, allow an interaction between the additive andsurface-deposited species (e.g., metal, metal-hydroxides,metal-oxyhyroxide, hydroxide, etc.), especially in the first fewformation cycles as the additive and surface-deposited species reactwith electrode surfaces. As such, various elements (e.g., Mg, Ni, Co,Mn), when used in combination with the low temperature treatment of theinvention, may have varying degrees of activity with additives such asLiDFOB, or others, and show similar or better performance improvementsdue to the formation of unique surfaces phases that may not be formedotherwise due to the combination of, and/or chemical/electrochemicalreactions between, surface components; for example, lithium/oxygenleached from the surfaces as in Example 1, surface/residual lithiumspecies (e.g., LiOH, Li₂CO₃) present in the starting metal oxides (e.g.,LLS) additives (e.g., LiDFOB), and coating elements (e.g., Mg, Ni, Co,Mn).

Example 7

Another unique aspect of the low temperature treatments described hereinis that they have been found to work with a combination several metallicelements. For example, FIG. 13, Panel (a), shows the capacity vs. cycleof the baseline LLS composition described in Example 6, treated with asolution of Al nitrate as described herein, with the addition of Mgnitrate, Ni nitrate, or Co nitrate in quantities described byAl_(1.85)Mg_(0.15)O_(x), Al_(1.85)Ni_(0.15)O_(x), andAl_(1.85)Co_(0.15)O₅, respectively (i.e., before possible reaction withleached/surface lithium, or additives). The data show that these examplecombinations are also able to improve the capacity retention of the LLSmaterials. In addition, as shown in FIG. 13, Panel (b), the ratecapability (% retention of ˜C/12 capacity) as a function of increasingdischarge rate is better than the untreated baseline for all threesamples.

Electrochemical Cells and Batteries.

A detailed schematic illustration of an electrochemical cell 10 of theinvention is shown in FIG. 14. Cell 10 comprises negative electrode 12separated from positive electrode 16 by an electrolyte 14, all containedin insulating housing 18 with suitable terminals (not shown) beingprovided in electronic contact with negative electrode 12 and positiveelectrode 16. Negative electrode 12 comprises an active material such asgraphite or the surface-treated lithium metal oxide described herein.Positive electrode 16 comprises metallic collector plate 15 and activelayer 17 comprising a lithium metal oxide material, such as thesurface-treated lithium metal oxide material described herein. Bindersand other materials, such as carbon, normally associated with both theelectrolyte and the negative and positive electrodes are well known inthe art and are not described herein, but are included as is understoodby those of ordinary skill in this art. FIG. 15 provides a schematicillustration of one example of a battery in which two strings ofelectrochemical sodium cells 10, described above, are arranged inparallel, each string comprising three cells 10 arranged in series.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein can be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the inventionand does not pose a limitation on the scope of the invention unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

Embodiments of the invention in which an exclusive property or privilegeis claimed as defined as follows:
 1. An electrode for a non-aqueouselectrochemical cell comprising an active lithium metal oxide materialcoated on a current collector; wherein the active lithium metal oxidematerial is prepared by a method comprising the sequential steps of: (a)contacting a first lithium metal oxide material with an aqueous acidicsolution containing one or more metal cations; and (b) heating theso-contacted first lithium metal oxide material from step (a) to drynessat a temperature below 200° C. to form the active lithium metal oxidematerial; wherein the metal cations in the aqueous acidic solutioncomprise one or more metal cations selected from the group consisting ofan alkaline earth metal ion, a transition metal ion, and aluminum ion;and wherein the first lithium metal oxide material in step (a) comprisesa compound with a structurally-integrated layered-layered structurecomprising xLi₂MnO₃.(1−x) LiMO₂ or a layered-layered-spinel structurecomprising y[xLi₂MnO₃.(1−x)LiMO₂].(1−y)LiM″₂O₄, in which M and M″comprise one or more metal ions for 0<x<1 and 0<y<1.
 2. The electrode ofclaim 1, wherein M and M″ comprise one or more metal ions selected fromthe group consisting of Mn, Ni, and Co cations, and optionally, one ormore other metal ions selected from the group consisting of Al, Mg andLi cations.
 3. The electrode of claim 1, wherein the active lithiummetal oxide material comprises Mn and Ni in an atomic ratio of Mn:Nigreater than or equal to
 1. 4. The electrode of claim 1, wherein theactive lithium metal oxide material comprises Mn, Ni and Co in an atomicratio of Mn:(Ni+Co) greater than or equal to
 1. 5. The electrode ofclaim 1, wherein the aqueous acidic solution comprises aluminum ion andthe active lithium metal oxide material exhibits a peak of about 531.5eV adjacent to a peak at about 529.5 eV in an XPS spectrum of thematerial.
 6. An electrochemical cell comprising a cathode, an anode, aseparator membrane between the cathode and the anode, and alithium-containing electrolyte contacting the anode, the cathode, andthe membrane, wherein either the cathode or the anode is the electrodeof claim
 1. 7. The electrochemical cell of claim 6, wherein theelectrolyte comprises up to about 1 percent by weight of lithiumdifluoro(oxalate)borate (LiDFOB).
 8. A battery containing more than oneelectrochemical cell of claim 7, connected in series, in parallel, or inboth series and parallel.